Molecular triads composed of ferrocene, C60, and nitroaromatic entities: electrochemical, computational, and photochemical investigations

dc.contributorWichita State University. Department of Chemistryen_US
dc.contributor.authorZandler, Melvin E.en_US
dc.contributor.authorSmith, Phillip M.en_US
dc.contributor.authorFujitsuka, Mamoruen_US
dc.contributor.authorIto, Osamuen_US
dc.contributor.authorD'Souza, Francisen_US
dc.coverage.spacialUnited Statesen_US
dc.descriptionFull text of this article is not available in SOAR.en_US
dc.description.abstractSynthesis and physicochemical characterization of a series of molecular triads composed of ferrocene, C(60), and nitroaromatic entities are reported. Electrochemical studies revealed multiple redox processes involving all three redox active ferrocene, C(60), and nitrobenzene entities. Up to eight redox couples within the accessible potential window of o-dichlorobenzene containing 0.1 M (TBA)ClO(4) are observed. A comparison between the measured redox potentials with those of the starting compounds revealed absence of any significant electronic interactions between the different redox entities. The geometric and electronic structure of the triads are elucidated by using ab initio B3LYP/3-21G methods. In the energy-optimized structures, as predicted by electrochemical studies, the first HOMO orbitals are found to be located on the ferrocene entity, while the first LUMO orbitals are mainly on the C(60) entity. The coefficients of the subsequent LUMO orbitals track the observed site of electrochemical reductions of the triads. The photochemical events of the triads are probed by both steady-state and time-resolved techniques. The steady-state emission intensities of the triads and the starting dyad, 2-(ferrocenyl)fulleropyrrolidine, are found to be completely quenched compared to fulleropyrrolidine bearing no redox active substituents. The subpicosecond and nanosecond transient absorption spectral studies revealed efficient charge separation (and rapid charge recombination) in the triads, and this has been attributed to the close spacing of the redox entities of the triad to one another.en_US
dc.description.versionpeer revieweden_US
dc.identifier.citationThe Journal of organic chemistry. 2002 Dec 27; 67(26): 9122-9.en_US
dc.publisherJohn Wiley and Sonsen_US
dc.relation.ispartofseriesThe Journal of organic chemistryen_US
dc.relation.ispartofseriesJ. Org. Chem.en_US
dc.rights.holderCopyright © 2003 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheimen_US
dc.subjectComparative Studyen_US
dc.subjectResearch Support, Non-U.S. Gov'ten_US
dc.subjectResearch Support, U.S. Gov't, Non-P.H.S.en_US
dc.subjectResearch Support, U.S. Gov't, P.H.S.en_US
dc.subject.meshComputational Biologyen_US
dc.subject.meshFerrous Compounds/chemistryen_US
dc.subject.meshModels, Molecularen_US
dc.subject.meshMolecular Conformationen_US
dc.subject.meshMolecular Structureen_US
dc.subject.meshNitro Compounds/chemistryen_US
dc.subject.meshPolycyclic Hydrocarbons, Aromatic/chemistryen_US
dc.subject.meshSpectrophotometry, Ultravioleten_US
dc.subject.meshTime Factorsen_US
dc.titleMolecular triads composed of ferrocene, C60, and nitroaromatic entities: electrochemical, computational, and photochemical investigationsen_US